EP0459951A2 - Char forming nonhalogenated flame retardant epoxy composition - Google Patents

Char forming nonhalogenated flame retardant epoxy composition Download PDF

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Publication number
EP0459951A2
EP0459951A2 EP91810389A EP91810389A EP0459951A2 EP 0459951 A2 EP0459951 A2 EP 0459951A2 EP 91810389 A EP91810389 A EP 91810389A EP 91810389 A EP91810389 A EP 91810389A EP 0459951 A2 EP0459951 A2 EP 0459951A2
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Prior art keywords
epoxy resin
resin composition
composition according
component
anhydride
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German (de)
French (fr)
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EP0459951A3 (en
Inventor
Dean Tallak Behm
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to char forming nonhalogenated flame retardant epoxy compositions.
  • Epoxy resins have traditionally been made flame retardant through the use of halogenated additives or resins.
  • bromine-containing organic compounds as flame retardants in polymer systems.
  • These known bromine-containing flame retardants are, conventionally, brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers or polyols.
  • These compounds are generally used in conjunction with a synergist, in particular antimony oxide, in order that lower levels of the bromine-containing compound can be employed, while maintaining a satisfactory level of flame retardant activity.
  • nonhalogenated flame retardant epoxy compositions As halogenated flame retardant epoxy compositions produce toxic fumes upon ignition. Flame retardancy of epoxy systems is possible with an anhydride cure and flame retardant additive, but without char formation. Char formation is recognized as an important factor in imparting flame retardancy.
  • nonhalogenated flame retardant epoxy compositions of the present invention comprising a multifunctional epoxide component, a modified polyamide hardener and one or more nonhalogenated flame retardants provide epoxy systems with improved flame retardancy without the addition of traditional halogenated flame retardants and result in char formation upon ignition.
  • the modified polyamide hardener contributes to the flame retardancy by forming an intumescent char when an epoxy system containing it in combination with a flame retardant is ignited.
  • the modified polyamide hardener allows for a one-component room temperature stable system, in addition to being flame retardant.
  • Aliphatic polyamines such as diethylenetriamine and triethylenetetramine have been used to provide char formation in two part epoxy systems, but such are not suitable in one part epoxy systems.
  • a further object of the present invention is to provide a one-component room temperature stable epoxy system.
  • the present invention relates to a one component epoxy resin composition
  • a one component epoxy resin composition comprising:
  • the multifunctional epoxide component can be selected from a broad range of aliphatic and aromatic epoxies having a functionality of at least two and comprises one or more epoxy resins.
  • Typical materials include diglycidyl ether of bisphenol A, epoxy phenol novolacs, 1,4-butane diol diglycidyl ether, epoxy cresol novolacs, trimethylolpropane triglycidyl ether, triglycidyl para-amino phenol, triglycidyl tris(p-hydroxyphenyl)methane, tetraglycidyl-1,1,2,2 tetrakis (p-hydroxyphenyl)ethane, vinyl cyclohexene dioxide, N,N,N1,N1-tetraglycidyl-4,41 methylene bis-benzeneamine, N,N,N1N1-tetraglycidyl metaxylene diamine, diglycidyl aniline, re
  • Preferred components correspond to wherein R is hydrogen or methyl, and n is 0.2-3.4. These components are exemplified by the epoxidation products of cresol novolacs and phenol novolacs of varying molecular weight. The preparation of such materials is well-known in the art.
  • the multifunctional epoxide component can be used in the composition of the present invention in an amount of from about 40 to about 73% by weight, preferably from about 48 to about 65% by weight.
  • the hardener is a product obtained by the reaction of approximately equimolar proportions of an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, polyazelaic anhydride, succinic anhydride and dodecenylsuccinic anhydride with a polyamine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, 1,3-diaminopropane, 1,6-diaminohexane, imino bis(propylamine) and methyl imino bis(propylamine) at a temperature of from about 50°C to about 160°C in an non-aqueous medium.
  • an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
  • the hardener is a product obtained as set forth hereinabove wherein the anhydride is phthalic anhydride and the amine is diethylene triamine.
  • the preparation of such materials is described in U.S. Patent No. 3,639,657, which is hereby incorporated by reference.
  • the hardener can be used in the composition of the present invention in an amount ranging from about 21 to about 45 parts per hundred, preferably about 22 to about 33 parts per hundred based on the multifunctional epoxide component.
  • Suitable nonhalogenated flame retardants are the oxides, sulphides, sulphates, and borates of tin, iron, molybdenum, zinc and antimony, e.g. tin oxide, iron oxide, molybdenum oxide, zinc oxide, antimony oxide and zinc borate; phosphorus-containing esters and salts e.g.
  • Preferred nonhalogenated flame retardants are ammonium polyphosphate, dimethyl methyl phosphonate, triarylphosphate, and cyclic phosphonate esters, most preferably, ammonium polyphosphate and encapsulated ammonium polyphosphate.
  • the flame retardant is conveniently employed in the composition of the present invention in an amount within the range of from about 8 to about 25% by weight, preferably about 10 to about 18% by weight.
  • composition of the present invention may additionally contain additional latent curing agents such as dicyandiamide; ANCAMINE® 2014AS, a modified polyamide from Pacific Anchor, MMB 2074, phenol novolac/pentamethyl diethylenetriamine from CIBA-GEIGY Corporation and the like.
  • additional latent curing agent is dicyandiamide.
  • the amount of said latent curing agent is from about 4 to about 13 parts per hundred, preferably about 7 to about 10 parts per hundred based on the multifunctional epoxide component and the amount of hardener component (b) is about 4 to about 13 parts per hundred, preferably about 7 to about 10 parts per hundred based on the multifunctional epoxide component.
  • compositions of the invention may also contain other conventional modifiers such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticizers, tackifiers, rubbers, diluents, and the like.
  • fillers which can be employed in the compositions according to the invention there may be mentioned, for example: glass fibers, glass balloons, boron fibers, carbon fibers, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, quartz powder, gypsum, antimony trioxide, bentones, talc, silica aerogel ("Aerosil"), fumed silica, lithopone, barite, calcium carbonate, titanium dioxide, carbon black, graphite, iron oxide, or metal powders such as aluminum powder or iron powder.
  • the preferred fillers are glass balloons and fumed silica. It is also possible to add other usual additives, for example, agents for conferring thixotropy, flow control agents such as silicones, cellulose acetate butyrate, polyvinyl butyral, stearates and the like.
  • a vertical type high-speed agitator, kneading machine, roll machine, ball mill or any other suitable mixing and agitating machine may be used for dispersion of the components of the composition of the present invention.
  • the cured epoxy compositions of the present invention exhibit a compression strength at 25°C of greater than 6500 psi.
  • the epoxy compositions of the present invention are particularly useful for the preparation of structures for the aerospace industry.
  • the epoxy resin and DMMP were blended together.
  • HT 939 was added and dispersed.
  • the ammonium polyphosphate was next added and dispersed.
  • the fumed silica was added and blended.
  • the glass balloons were added and blended.
  • the epoxy resins were heat blended at 70°C.
  • the blend was allowed to cool to room temperature and the DMMP was next added and blended.
  • HT 939 was then added and dispersed, followed by the ammonium polyphosphate and then the silica fume was blended in.
  • the glass beads were added and blended.
  • compositions were pressed between 2 pieces of glass precoated with a release agent (MONO-COAT E205 from Chem-Trend Incorporated) to 0.3175 cm thickness and heated 1.5 hours at 121°C.
  • the samples were then removed from the glass plates, cut and burned according to Federal Aviation Requirement 25.853. The results are provided in Table 3.
  • Example 2 The procedure of Example 2 was repeated utilizing the following components:
  • compositions were de-aired and then pressed between 2 pieces of glass precoated with a release agent (MONO-COAT E205 from Chem-Trend Incorporated) to a thickness of 0.3175 cm and heated 1.5 hours at 121°C.
  • a release agent (MONO-COAT E205 from Chem-Trend Incorporated) from Chem-Trend Incorporated) to a thickness of 0.3175 cm and heated 1.5 hours at 121°C.
  • the samples were then removed from the glass plates, cut and burned according to Federal Aviation Requirement 25.853. The results are provided in Table 5.
  • the ingredients of the epoxy resin prepared in this example are provided in Table 6.
  • the epoxy resins were added together and blended.
  • the fumed silica was then added and blended, followed by addition and dispersion of the HT 9506, the blending in of the triarylphosphate, the dispersion of the ammonium polyphosphate and lastly blending in of the glass beads.
  • compositions were then cured and tested as set forth in Examples 2 and 3. The results are provided in Table 7.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present application relates to a one component epoxy resin composition comprising:
  • a) a multifunctional epoxide component,
  • b) a hardener obtained by the reaction of approximately equimolar proportions of an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, polyazelaic anhydride, succinic anhydride and dodecenylsuccinic anhydride with polyamine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, 1,3-diaminopropane, 1,6-diaminohexane, imino bis(propylamine) and methyl imino bis(propylamine) and
  • c) one or more nonhalogenated flame retardants.

Description

  • The present invention relates to char forming nonhalogenated flame retardant epoxy compositions.
  • Epoxy resins have traditionally been made flame retardant through the use of halogenated additives or resins. For example, it is known to use bromine-containing organic compounds as flame retardants in polymer systems. These known bromine-containing flame retardants are, conventionally, brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers or polyols. These compounds are generally used in conjunction with a synergist, in particular antimony oxide, in order that lower levels of the bromine-containing compound can be employed, while maintaining a satisfactory level of flame retardant activity.
  • Due to increasing restrictions on the flammability and toxicity of materials, for example in the production of aircraft interiors, there is a need for nonhalogenated flame retardant epoxy compositions as halogenated flame retardant epoxy compositions produce toxic fumes upon ignition. Flame retardancy of epoxy systems is possible with an anhydride cure and flame retardant additive, but without char formation. Char formation is recognized as an important factor in imparting flame retardancy.
  • Surprisingly, the char forming nonhalogenated flame retardant epoxy compositions of the present invention comprising a multifunctional epoxide component, a modified polyamide hardener and one or more nonhalogenated flame retardants provide epoxy systems with improved flame retardancy without the addition of traditional halogenated flame retardants and result in char formation upon ignition. The modified polyamide hardener contributes to the flame retardancy by forming an intumescent char when an epoxy system containing it in combination with a flame retardant is ignited. The modified polyamide hardener allows for a one-component room temperature stable system, in addition to being flame retardant.
  • Epoxy systems containing only the modified polyamide hardener and no flame retardant exhibits no flame retardancy. Therefore, there appears to be a nitrogen-phosphorus synergism which is responsible for the flame retardancy of the systems. Flame retardancy and some char formation is possible with an epoxy system containing dicyanodiamide and ammonium phosphate but without the heavy char formation seen with the modified polyamide hardener of the present invention.
  • Aliphatic polyamines, such as diethylenetriamine and triethylenetetramine have been used to provide char formation in two part epoxy systems, but such are not suitable in one part epoxy systems.
  • Accordingly, it is a primary object of the present invention to provide a one component char forming epoxy system without the use of halogenated flame retardants.
  • A further object of the present invention is to provide a one-component room temperature stable epoxy system.
  • The present invention relates to a one component epoxy resin composition comprising:
    • a) a multifunctional epoxide component,
    • b) a hardener obtained by the reaction of approximately equimolar proportions of an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, polyazelaic anhydride, succinic anhydride and dodecenylsuccinic anhydride with polyamine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, 1,3-diaminopropane, 1,6-diaminohexane, imino bis(propylamine) and methyl imino bis(propylamine) and
    • c) one or more nonhalogenated flame retardants.
  • The multifunctional epoxide component can be selected from a broad range of aliphatic and aromatic epoxies having a functionality of at least two and comprises one or more epoxy resins. Typical materials include diglycidyl ether of bisphenol A, epoxy phenol novolacs, 1,4-butane diol diglycidyl ether, epoxy cresol novolacs, trimethylolpropane triglycidyl ether, triglycidyl para-amino phenol, triglycidyl tris(p-hydroxyphenyl)methane, tetraglycidyl-1,1,2,2 tetrakis (p-hydroxyphenyl)ethane, vinyl cyclohexene dioxide, N,N,N¹,N¹-tetraglycidyl-4,4¹ methylene bis-benzeneamine, N,N,N¹N¹-tetraglycidyl metaxylene diamine, diglycidyl aniline, resorcinol diglycidyl ether, the diglycidyl ethers of catechol, hydroquinone, and the like, diglycidyl ortho-toluidine, diglycidyl isophthalate, bisphenol F and S epoxy resins, triglycidyl isocyanurate, epoxidized hydantoin resin, and N,N,N¹,N¹-tetraglycidyl 1,3 bis-amino-methylcyclohexane. The various ethers may be substituted on the respective phenyl rings by such non-reactive substituents as alkyl, halogen, and the like.
  • Preferred components correspond to
    Figure imgb0001
    wherein R is hydrogen or methyl, and n is 0.2-3.4. These components are exemplified by the epoxidation products of cresol novolacs and phenol novolacs of varying molecular weight. The preparation of such materials is well-known in the art.
  • (b) diglycidyl ethers of bisphenols corresponding to the formula
    Figure imgb0002
    wherein m is 0-50 and X is -CH₂-,
    Figure imgb0003
  • These represent, respectively, bisphenols F, A and S.
  • (c) 1,4-butanediol diglycidyl ether.
  • The multifunctional epoxide component can be used in the composition of the present invention in an amount of from about 40 to about 73% by weight, preferably from about 48 to about 65% by weight.
  • The hardener is a product obtained by the reaction of approximately equimolar proportions of an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, polyazelaic anhydride, succinic anhydride and dodecenylsuccinic anhydride with a polyamine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, 1,3-diaminopropane, 1,6-diaminohexane, imino bis(propylamine) and methyl imino bis(propylamine) at a temperature of from about 50°C to about 160°C in an non-aqueous medium.
  • Preferably, the hardener is a product obtained as set forth hereinabove wherein the anhydride is phthalic anhydride and the amine is diethylene triamine. The preparation of such materials is described in U.S. Patent No. 3,639,657, which is hereby incorporated by reference.
  • The hardener can be used in the composition of the present invention in an amount ranging from about 21 to about 45 parts per hundred, preferably about 22 to about 33 parts per hundred based on the multifunctional epoxide component.
  • Suitable nonhalogenated flame retardants are the oxides, sulphides, sulphates, and borates of tin, iron, molybdenum, zinc and antimony, e.g. tin oxide, iron oxide, molybdenum oxide, zinc oxide, antimony oxide and zinc borate; phosphorus-containing esters and salts e.g. trialkyl and triarylphosphates, alkylarylphosphates and ammonium polyphosphates; metal hydrates, especially hydrated alumina; and the dehydropolymers of compounds of mono-, di- or tri-substituted benzene, the substituents being a C₅- and/or C₆-cycloaliphatic hydrocarbon, especially 1,1-diphenyl-bicyclohexyl or 1,1-diphenylbicyclopentyl. Preferred nonhalogenated flame retardants are ammonium polyphosphate, dimethyl methyl phosphonate, triarylphosphate, and cyclic phosphonate esters, most preferably, ammonium polyphosphate and encapsulated ammonium polyphosphate.
  • The flame retardant is conveniently employed in the composition of the present invention in an amount within the range of from about 8 to about 25% by weight, preferably about 10 to about 18% by weight.
  • The composition of the present invention may additionally contain additional latent curing agents such as dicyandiamide; ANCAMINE® 2014AS, a modified polyamide from Pacific Anchor, MMB 2074, phenol novolac/pentamethyl diethylenetriamine from CIBA-GEIGY Corporation and the like. The preferred additional latent curing agent is dicyandiamide.
  • When used, the amount of said latent curing agent is from about 4 to about 13 parts per hundred, preferably about 7 to about 10 parts per hundred based on the multifunctional epoxide component and the amount of hardener component (b) is about 4 to about 13 parts per hundred, preferably about 7 to about 10 parts per hundred based on the multifunctional epoxide component.
  • The compositions of the invention may also contain other conventional modifiers such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticizers, tackifiers, rubbers, diluents, and the like. As extenders, reinforcing agents, fillers and pigments which can be employed in the compositions according to the invention there may be mentioned, for example: glass fibers, glass balloons, boron fibers, carbon fibers, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, quartz powder, gypsum, antimony trioxide, bentones, talc, silica aerogel ("Aerosil"), fumed silica, lithopone, barite, calcium carbonate, titanium dioxide, carbon black, graphite, iron oxide, or metal powders such as aluminum powder or iron powder. The preferred fillers are glass balloons and fumed silica. It is also possible to add other usual additives, for example, agents for conferring thixotropy, flow control agents such as silicones, cellulose acetate butyrate, polyvinyl butyral, stearates and the like.
  • A vertical type high-speed agitator, kneading machine, roll machine, ball mill or any other suitable mixing and agitating machine may be used for dispersion of the components of the composition of the present invention.
  • The cured epoxy compositions of the present invention exhibit a compression strength at 25°C of greater than 6500 psi.
  • The epoxy compositions of the present invention are particularly useful for the preparation of structures for the aerospace industry.
  • The following examples will further illustrate the embodiments of the instant invention.
    • Example 1
  • This example illustrates the preparation of a typical composition of the present invention. The ingredients are listed in Table 1.
    Figure imgb0004
  • Initially, 200 g of the epoxy resin was blended with the hardener, ammonium polyphosphate and dimethyl methyl phosphonate. The remaining epoxy resin was added and blended using the Ross LOM Double Planetary mixer for 15 minutes. The glass balloons were added and the mixture blended for an additional 15 minutes. The specific gravity of the resulting composition was 0.68 g/ml and the press flow was 100 g/min which was measured on a Castor Severs Extrusion Rheometer at 80 psi and 25°C with a 125 ml orifice.
    • Examples 2 and 3
  • These examples illustrate the preparation of additional compositions of the present invention and an evaluation of the flame retardancy of the composition. The ingredients are listed in Table 2.
    Figure imgb0005
  • For example 2, the epoxy resin and DMMP were blended together. HT 939 was added and dispersed. The ammonium polyphosphate was next added and dispersed. Then, the fumed silica was added and blended. Lastly, the glass balloons were added and blended.
  • For example 3, the epoxy resins were heat blended at 70°C. The blend was allowed to cool to room temperature and the DMMP was next added and blended. HT 939 was then added and dispersed, followed by the ammonium polyphosphate and then the silica fume was blended in. Lastly, the glass beads were added and blended.
  • The resulting compositions were pressed between 2 pieces of glass precoated with a release agent (MONO-COAT E205 from Chem-Trend Incorporated) to 0.3175 cm thickness and heated 1.5 hours at 121°C. The samples were then removed from the glass plates, cut and burned according to Federal Aviation Requirement 25.853. The results are provided in Table 3.
    Figure imgb0006
    • Examples 4 and 5
  • The procedure of Example 2 was repeated utilizing the following components:
    Figure imgb0007
  • The resulting compositions were de-aired and then pressed between 2 pieces of glass precoated with a release agent (MONO-COAT E205 from Chem-Trend Incorporated) to a thickness of 0.3175 cm and heated 1.5 hours at 121°C. The samples were then removed from the glass plates, cut and burned according to Federal Aviation Requirement 25.853. The results are provided in Table 5.
    Figure imgb0008
    • Examples 6 and 7
  • The ingredients of the epoxy resin prepared in this example are provided in Table 6.
    Figure imgb0009
  • The epoxy resins were added together and blended. The fumed silica was then added and blended, followed by addition and dispersion of the HT 9506, the blending in of the triarylphosphate, the dispersion of the ammonium polyphosphate and lastly blending in of the glass beads.
  • The compositions were then cured and tested as set forth in Examples 2 and 3. The results are provided in Table 7.
    Figure imgb0010

Claims (20)

  1. A one component epoxy resin composition comprising:
    a) a multifunctional epoxide component,
    b) a hardener obtained by the reaction of approximately equimolar proportions of an anhydride selected from the group consisting of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, polyazelaic anhydride, succinic anhydride and dodecenylsuccinic anhydride with polyamine selected from the group consisting of ethylene diamine, diethylene tne, triethylene tetramine, 1,3-diaminopropane, 1,6-diaminohexane, imino bis(propylamine) and methyl imino bis(propylamine) and
    c) one or more nonhalogenated flame retardants.
  2. A one component epoxy resin composition according to claim 1 wherein the multifunctional epoxide component comprises at least one aliphatic or aromatic epoxide having a functionality of at least two.
  3. A one component epoxy resin composition according to claim 1 wherein said multifunctional epoxide component comprises at least one epoxy resin selected from the group consisting of diglycidyl ether of bisphenol A, epoxy phenol novolacs, 1,4-butane diol diglycidyl ether, epoxy cresol novolacs, trimethylolpropane triglycidyl ether, triglycidyl para-amino phenol, triglycidyl tris(p-hydroxyphenyl)methane, tetraglycidyl-1,1,2,2 tetrakis (p-hydroxyphenyl)ethane, vinyl cyclohexene dioxide, N,N,N¹,N¹-tetraglycidyl-4,4¹ methylene bis-benzeneamine, N,N,N¹N¹-tetraglycidyl metaxylene diamine, diglycidyl aniline, resorcinol diglycidyl ether, the diglycidyl ethers of catechol, hydroquinone, and the like, diglycidyl ortho-toluidine, diglycidyl isophthalate, bisphenol F and S epoxy resins, triglycidyl isocyanurate, epoxidized hydantoin resin and N,N,N¹,N¹-tetraglycidyl 1,3 bis-amino-methylcyclohexane.
  4. A one component epoxy resin composition according to claim 1 wherein said multifunctional epoxide component comprises at least one epoxy resin selected from the group consisting of
    Figure imgb0011
     wherein R is hydrogen or methyl, and n is 0.2-3.4; and
    (b) diglycidyl ethers of bisphenols corresponding to the formula
    Figure imgb0012
     wherein m is 0-50 and X is -CH₂-,
    Figure imgb0013
  5. A one component epoxy resin composition according to claim 1 wherein the multifunctional epoxide component comprises at least one epoxy resin selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, epoxy phenol novolac resin, and triglycidyl para-amino phenol resin.
  6. A one component epoxy resin composition according to claim 1 wherein the multifunctional epoxide component is present in an amount ranging from about 40 to 73% by weight.
  7. A one component epoxy resin composition according to claim 1 wherein the multifunctional epoxide component is present in an amount ranging from about 48 to 65% by weight.
  8. A one component epoxy resin composition according to claim 1 wherein the hardener comprises phthalic anhydride and diethylene triamine.
  9. A one component epoxy resin composition according to claim 1 wherein the hardener is present in an amount ranging from about 21 to 45 parts per hundred based upon the multifunctional epoxide component.
  10. A one component epoxy resin composition according to claim 1 wherein the hardener is present in an amount ranging from about 22 to 33 parts per hundred based upon the multifunctional epoxide component.
  11. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are selected from the group consisting of oxides, sulphides, suphates and borates of tin, iron, molybdenum, zinc and antimony; phosphorus-containing esters and salts; metal hydrates and the dehydropolymers of compounds of mono-, di- or tri-substituted benzene, the substituents being a C₅- or C₆-cycloaliphatic hydrocarbon.
  12. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are selected from the group consisting of tin oxide, iron oxide, molybdenum oxide, zinc oxide, antimony oxide and zinc borate, trialkylphosphate, triarylphosphates, alkylarylphosphates, ammonium polyphosphates, hydrated alumina, dehydropolymers of 1,1-diphenyl-bicyclohexyl or 1,1-diphenylbicyclopentyl substituted benzene.
  13. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are selected from the group consisting of ammonium polyphosphate, dimethyl methyl phosphonate, triarylphosphonate and cyclic phosphonate esters.
  14. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are selected from the group consisting of ammonium polyphosphate and dimethyl methyl phosphonate.
  15. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are present in an amount of from about 8 to about 25% by weight.
  16. A one component epoxy resin composition according to claim 1 wherein said nonhalogenated flame retardants are present in an amount of from about 10 to 18% by weight.
  17. A one component epoxy resin composition according to claim 1 further comprising an additional latent curing agent.
  18. A one component epoxy resin composition according to claim 1 further comprising an additional latent curing agent selected from the group consisting of dicyandiamide and phenol novolac/pentamethyl diethylenetriamine.
  19. A one component epoxy resin composition according to claim 17 wherein said additional latent curing agent is present in an amount ranging from about 4 to about 13 parts per hundred based upon the multifunctional epoxide component and said hardener is present in an amount ranging from about 4 to about 13 parts per hundred based upon the multifunctional epoxide component.
  20. A one component epoxy resin composition according to claim 1 further comprising one or more fillers.
EP19910810389 1990-05-30 1991-05-22 Char forming nonhalogenated flame retardant epoxy composition Withdrawn EP0459951A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53068990A 1990-05-30 1990-05-30
US530689 1990-05-30

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EP0459951A2 true EP0459951A2 (en) 1991-12-04
EP0459951A3 EP0459951A3 (en) 1993-09-15

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EP (1) EP0459951A3 (en)
JP (1) JPH04227923A (en)
CA (1) CA2043377A1 (en)

Cited By (12)

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WO1995011272A1 (en) * 1993-10-21 1995-04-27 ISOVOLTA Österreichische Isolierstoffwerke Aktiengesellschaft Halogen-free resin mixture, a self-extinguishing prepreg containing this mixture and the use of such a prepreg
EP0705869A1 (en) * 1994-09-06 1996-04-10 Hoechst Aktiengesellschaft Flame retardant epoxy resin moulding compositions
GB2264262B (en) * 1992-02-18 1996-04-24 Pilkington Plc Impact resistant laminate and manufacture thereof
US5700575A (en) * 1993-12-27 1997-12-23 Chisso Corporation Water-insoluble ammonium polyphosphate particles
CN1073127C (en) * 1995-09-29 2001-10-17 东芝化学株式会社 Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same
US6359038B1 (en) * 1996-05-21 2002-03-19 Abb Power T&D Company Inc. Arc-quenching fuse tubes
WO2006085494A1 (en) * 2005-02-08 2006-08-17 Showa Denko K.K. Flame-retardant composition for solder resist and use thereof
US8188165B2 (en) 2004-12-23 2012-05-29 3M Innovative Properties Company Fire-retardant low-density epoxy composition
EP2970651A4 (en) * 2013-03-15 2016-09-21 Plasma Systems Holdings Inc MULTIFUNCTIONAL CASTING EPOXY RESIN SYSTEM
WO2021094292A1 (en) 2019-11-13 2021-05-20 Zephyros, Inc. Potting paste for honeycomb reinforcement
CN117511352A (en) * 2023-11-29 2024-02-06 北京天乙长科技发展有限公司 An anti-corrosion low-viscosity solvent-free coating for oil well pipes and its preparation method and application
CN120425612A (en) * 2025-05-06 2025-08-05 山东四达工贸股份有限公司 Preparation method of halogen-free flame-retardant phenolic laminated paperboard

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US5955184A (en) * 1995-09-29 1999-09-21 Toshiba Chemical Corporation Halogen-free flame-retardant epoxy resin composition as well as prepreg and laminate containing the same
US6214455B1 (en) 1995-09-29 2001-04-10 Toshiba Chemical Corporation Bisphenol A and novolak epoxy resins with nitrogen-containing phenolic resin
JP6222428B2 (en) * 2013-07-05 2017-11-01 ナガセケムテックス株式会社 Epoxy resin composition

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US3639657A (en) * 1969-03-19 1972-02-01 Ciba Geigy Corp Products of acid anhydrides and polyamines used as latent hardeners for epoxy resins
DE2050130A1 (en) * 1970-10-13 1972-04-20 Knapsack Ag Rigid polyepoxy resin foams containing flame retardants and process for their production
US4145369A (en) * 1976-09-20 1979-03-20 Hitachi, Ltd. Flame-retardant epoxy resin compositions

Cited By (19)

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Publication number Priority date Publication date Assignee Title
GB2264262B (en) * 1992-02-18 1996-04-24 Pilkington Plc Impact resistant laminate and manufacture thereof
US5648436A (en) * 1993-10-21 1997-07-15 Isovolta Osterreichische Isolierstoffwerke Aktiengesellschaft Halogen-free mixture, a self-extinguishing prepreg containing this mixture and the use of such a prepreg
WO1995011272A1 (en) * 1993-10-21 1995-04-27 ISOVOLTA Österreichische Isolierstoffwerke Aktiengesellschaft Halogen-free resin mixture, a self-extinguishing prepreg containing this mixture and the use of such a prepreg
US5700575A (en) * 1993-12-27 1997-12-23 Chisso Corporation Water-insoluble ammonium polyphosphate particles
US5945467A (en) * 1993-12-27 1999-08-31 Chisso Corp. Flame-retardant thermosetting resin composition, water-insoluble ammonium polyphosphate particles and method for producing the particles
EP0705869A1 (en) * 1994-09-06 1996-04-10 Hoechst Aktiengesellschaft Flame retardant epoxy resin moulding compositions
CN1073127C (en) * 1995-09-29 2001-10-17 东芝化学株式会社 Hologen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same
US6359038B1 (en) * 1996-05-21 2002-03-19 Abb Power T&D Company Inc. Arc-quenching fuse tubes
US8188165B2 (en) 2004-12-23 2012-05-29 3M Innovative Properties Company Fire-retardant low-density epoxy composition
WO2006085494A1 (en) * 2005-02-08 2006-08-17 Showa Denko K.K. Flame-retardant composition for solder resist and use thereof
EP2970651A4 (en) * 2013-03-15 2016-09-21 Plasma Systems Holdings Inc MULTIFUNCTIONAL CASTING EPOXY RESIN SYSTEM
US9629254B2 (en) 2013-03-15 2017-04-18 Plasma Systems Holdings, Inc. Multi-function epoxy casting resin system
WO2021094292A1 (en) 2019-11-13 2021-05-20 Zephyros, Inc. Potting paste for honeycomb reinforcement
CN114981386A (en) * 2019-11-13 2022-08-30 泽费罗斯股份有限公司 Encapsulation paste for reinforcing honeycomb
US20220396719A1 (en) * 2019-11-13 2022-12-15 Zephyros, Inc. Potting Paste for Honeycomb Reinforcement
US12540259B2 (en) * 2019-11-13 2026-02-03 Zephyros, Inc. Potting paste for honeycomb reinforcement
CN117511352A (en) * 2023-11-29 2024-02-06 北京天乙长科技发展有限公司 An anti-corrosion low-viscosity solvent-free coating for oil well pipes and its preparation method and application
CN120425612A (en) * 2025-05-06 2025-08-05 山东四达工贸股份有限公司 Preparation method of halogen-free flame-retardant phenolic laminated paperboard
CN120425612B (en) * 2025-05-06 2025-11-11 山东四达工贸股份有限公司 A method for preparing halogen-free flame-retardant phenolic laminate paperboard

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Publication number Publication date
EP0459951A3 (en) 1993-09-15
CA2043377A1 (en) 1991-12-01
JPH04227923A (en) 1992-08-18

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